CN114671977B - Zwitterionic polymer hydrogel and preparation method and application thereof - Google Patents
Zwitterionic polymer hydrogel and preparation method and application thereof Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 90
- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 cationic imidazolium salt Chemical class 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 229940117986 sulfobetaine Drugs 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229960003237 betaine Drugs 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 125000004386 diacrylate group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000002280 amphoteric surfactant Substances 0.000 claims description 5
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 2
- RBWFVUDBNNXTFZ-UHFFFAOYSA-N 1h-imidazole;potassium Chemical compound [K].C1=CNC=N1 RBWFVUDBNNXTFZ-UHFFFAOYSA-N 0.000 claims description 2
- YNCPXBIZAPNQIJ-UHFFFAOYSA-N 1h-imidazole;sodium Chemical compound [Na].C1=CNC=N1 YNCPXBIZAPNQIJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 239000000523 sample Substances 0.000 description 21
- 239000011521 glass Substances 0.000 description 12
- 238000009864 tensile test Methods 0.000 description 10
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- 238000004458 analytical method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 230000009471 action Effects 0.000 description 2
- 229960001506 brilliant green Drugs 0.000 description 2
- HXCILVUBKWANLN-UHFFFAOYSA-N brilliant green cation Chemical compound C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 HXCILVUBKWANLN-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 150000008365 aromatic ketones Chemical group 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 1
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- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Medical Uses (AREA)
Abstract
The application discloses a zwitterionic polymer hydrogel and a preparation method and application thereof, wherein the zwitterionic polymer hydrogel is formed by crosslinking cationic imidazolium salt, a zwitterionic monomer and an amide compound through dynamic covalent bonds and non-covalent bonds; wherein the non-covalent bond includes electrostatic and hydrogen bonding. By constructing a more stable network structure, the mechanical strength of the hydrogel is improved, and the adhesiveness of the material is increased; endows the hydrogel with stretchability and self-repairing performance.
Description
Technical Field
The application relates to a zwitterionic polymer hydrogel and a preparation method and application thereof, and belongs to the technical field of hydrogels.
Background
Hydrogel is a typical soft and wet material, and is an excellent material for preparing the ionic skin strain sensor in the last decades of researches because of being a high polymer material, having softness, biocompatibility and a three-dimensional network structure. However, most hydrogels often have poor mechanical properties, and the gel is easy to break during repeated deformation or extrusion, so that the functionality of the gel is lost, and complex strain environments are difficult to meet. Meanwhile, the reliability and accuracy of sensor signal acquisition are extremely high in requirements on sensitivity and conductivity of the hydrogel. These factors greatly limit the practical use of zwitterionic hydrogels as strain sensors. Thus, durability and reliability may be improved by adding self-healing capability to repair damage to extend the life of the sensor in order to continuously maintain the integrity of the network structure. The conductive mode is carefully designed, so that the conductive network can respond to external micro strain to the greatest extent in the deformation process, and can recover in time, and high sensing performance and high sensitivity are obtained. The practical daily use of the ionic skin is maximally realized, and the most critical factors are that the material needs to have high strength, self-healing property and excellent electric conductivity.
Conventional hydrogels form three-dimensional networks by covalent cross-linking. However, the problem of uneven dispersion of covalent crosslinking points exists, which leads to uneven polymer network structure in the gel, and the gel is characterized by easy breakage and easy fracture in a macroscopic way. Such hydrogel networks also lack energy dissipation mechanisms. When the crack is acted by external stress, the energy at the crack cannot be effectively dissipated, and the crack is continuously diffused until the crack breaks. By adding graphite, carbon fibers, carbon nanotubes, metal particles and other such inorganic materials to the hydrogel, the conductive components can be uniformly distributed in the hydrogel network, thereby achieving high conductivity and colloidal stability of the hydrogel. In previous studies, to optimize the sum of these properties, it was generally necessary to add cumbersome and time-consuming manufacturing steps to the preparation of the polymer hydrogels, and even to control specific reaction temperatures and reaction times to initiate the radical polymerization. Therefore, in the flexible electronics field, it is a challenge to develop an ionic dermatological apparatus with as many good properties as possible using a simple gel preparation strategy.
Disclosure of Invention
According to one aspect of the application, the application provides a zwitterionic polymer hydrogel, which has good stretchability, plasticity, adhesiveness, conductivity and self-healing performance, and solves the problem that the conventional hydrogel has single performance and cannot meet the actual situation. The electrostatic effect and hydrogen bond effect of the cationic imidazole salt are utilized to endow the hydrogel with various performances such as stretchability, self-repairing property and the like, and the preparation method is simple and convenient.
A zwitterionic polymer hydrogel is formed by crosslinking cationic imidazole salt, a zwitterionic monomer and an amide compound through dynamic covalent bonds and non-covalent bonds.
Optionally, the non-covalent bond includes electrostatic and hydrogen bonding.
Optionally, the maximum strain of the zwitterionic polymer hydrogel can reach 1155% -1172%.
Optionally, the maximum stress of the zwitterionic polymer hydrogel is 337kPa to 346kPa.
The repair rate of the zwitterionic polymer hydrogel after 24 hours reaches 80 percent.
Optionally, the cationic imidazole salt is selected from at least one of cationic imidazole sodium salt and cationic imidazole potassium salt.
Optionally, the zwitterionic monomer is a betaine type amphoteric surfactant.
Optionally, the betaine type amphoteric surfactant is selected from one of carboxylic acid betaines and sulfobetaines.
Optionally, the carboxylic acid betaine is selected from one of methacrylic acid carboxybetaine and acryloylethyl carboxybetaine.
Optionally, the sulfobetaine is selected from one of sulfobetain methacrylate and acryloylethyl sulfobetaine.
By using the methacryloyl ethyl sulfobetaine, a more stable network structure can be constructed, the mechanical strength of the hydrogel can be improved, and the adhesiveness of materials can be increased.
Optionally, the amide compound is at least one selected from acrylamide and N-vinyl caprolactam.
According to yet another aspect of the present application, a method of preparing a zwitterionic polymer hydrogel is provided.
The preparation method of the zwitterionic polymer hydrogel comprises the following steps:
and (3) carrying out photoinitiation reaction on a mixture containing a zwitterionic monomer, an amide compound, a cross-linking agent, cationic imidazole and a photoinitiator to obtain the zwitterionic hydrogel.
Optionally, the cross-linking agent is selected from at least one of polyethylene glycol diacrylate and N, N' -methylenebisacrylamide.
Optionally, the photoinitiator is selected from aromatic ketones.
Optionally, the aromatic ketone compound is selected from at least one of 2-hydroxy-2-methyl-1-phenylpropion and 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropionacetone.
Optionally, the molar ratio of the cationic imidazole salt to the zwitterionic monomer to the amide compound is 1-2: 1-4:1-4.
Optionally, the cationic imidazole salt is added in the form of an aqueous solution thereof, and the concentration of the cationic imidazole salt in the aqueous solution is 1mol/L to 3mol/L.
Optionally, the amount of the cross-linking agent is 0.1% -0.5% of the molar total amount of the zwitterionic monomer and the amide compound.
Optionally, the percentage of the cross-linking agent in the molar total of the zwitterionic monomer and the amide-type compound is independently selected from any value or range of values between any two of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%.
Optionally, the photoinitiator is used in an amount of 0.1 to 0.5% of the molar sum of the zwitterionic monomer and the cationic imidazole salt.
Alternatively, the percent of the photoinitiator relative to the total molar amount of the zwitterionic monomer and the cationic imidazole salt is independently selected from any of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, or a range of values therebetween.
Alternatively, the conditions for photoinitiating the reaction are as follows:
the light source is ultraviolet light, and the wavelength of the ultraviolet light is 320 nm-365 nm;
the reaction time is 10 nm-20 min.
According to a third aspect of the present application there is provided the use of a zwitterionic polymer hydrogel in flexible electronic devices, wearable devices, stretchable bioelectronics, electronic test instrument stickers, medical adhesives.
The zwitterionic polymer hydrogel and/or the zwitterionic polymer hydrogel obtained by the preparation method are applied to flexible electronic equipment, wearable equipment, stretchable bioelectronic devices, electronic detection instrument adhesive patches and medical adhesives.
The application has the beneficial effects that:
1) The zwitterionic hydrogel provided by the application has multiple properties such as good stretchability, adhesiveness, self-repairing property and the like, and can be used for preparing products such as medical adhesives and the like; the hydrogel adhesion closely contacts the skin, and then the signal is perfectly conducted through the electric conduction performance. The adhesive sheet can be applied to flexible electronic equipment, wearable equipment, stretchable bioelectronics and electronic detection instrument adhesive sheets, and has wide application prospect.
2) The preparation method of the zwitterionic polymer hydrogel provided by the application is a one-step method and has the advantages of simplicity, high efficiency and improvement of crosslinking uniformity. The electrostatic action and hydrogen bonding action of the cationic imidazole salt are utilized to endow the hydrogel with various performances such as stretchability, self-repairing property and the like; by using the betaine type amphoteric surfactant (such as methacryloyl ethyl sulfobetaine), a more stable network structure can be constructed, the mechanical strength of the hydrogel can be improved, and the adhesiveness of materials can be increased.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a cationic imidazole salt used in the present application.
FIG. 2 is a drawing of a tensile test of a sample and a corresponding bar graph of elastic modulus and toughness for example 1 of the present application, wherein A is the tensile test of the sample and B is the bar graph of elastic modulus and toughness.
FIG. 3 is a drawing of a tensile test of a sample and a corresponding bar graph of elastic modulus and toughness for example 2 of the present application, wherein A is the tensile test of the sample and B is the bar graph of elastic modulus and toughness.
FIG. 4 is a graph showing the self-healing properties of the sample in example 2 of the present application, wherein A is a digital photograph of the self-healed hydrogel dyed with methyl orange and brilliant green, and B is a digital photograph of the healed hydrogel subjected to a tensile test.
FIG. 5 is a graph showing the conductivity and sensing properties of the sample of example 2 according to the present application, wherein A is a graph of the relative resistance change (ΔR/R0) of the hydrogel during stretching, and B is a graph of the relative resistance change of the hydrogel stretched 150 times at 20% strain.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Specifically, the synthesis procedure of the cationic imidazolium salt in this experiment is as follows:
n '- (3-chloropropyl) -N' -methylurea (11.5 g,1.53 mol) and 1-vinylimidazole (7.9 g,1.67 mol) were dissolved in 50mL of acetone. The reaction mixture was refluxed with stirring at 70℃for 24h. The solvent was removed by rotary evaporation under reduced pressure, and the crude product obtained was washed 3 times with diethyl ether. After the product is dried in vacuum at room temperature, chloroform/methane (10:1, v/v) mixture is used as eluent, and further purification is carried out through silica gel column chromatography, so that yellow viscous liquid with the purity of transparency (the yield is approximately equal to 70%) is obtained, namely the required cationic imidazole monomer.
Other materials in the examples of the present application were purchased commercially, wherein:
methacryloyl ethyl Sulfobetaine (SBMA), AR >99% (national medicine control Strand chemical Co., ltd.).
Acrylamide (AM), analytically pure AR (national medicine control chemical company, inc.).
Polyethylene glycol diacrylate (PEGDA), AR >99% (Shanghai aladine Biochemical technologies Co., ltd.).
2-hydroxy-2-methyl-1-phenylpropion with R >99% (Shanghai Ala Biochemical technologies Co., ltd.).
The analysis method in the embodiment of the application is as follows:
nuclear magnetic resonance analysis was performed using a Bruker DRX 400NMR spectrometer.
Stretching analysis was performed using a universal stretcher.
The conductivity analysis was performed using a digital four-probe tester (ST 2258C, china).
The tensile strain was calculated as follows:
wherein L is the stretched length of the sample; l (L) 0 Is the initial length of the sample.
The fracture stress is calculated as follows:
wherein F is a load N; a is that 0 Is the cross-sectional area of the sample.
Example 1
0.6g of imidazole cation salt is weighed at room temperature, 3.9ml of water is added to prepare 1mol/L solution, 0.42g SBMA,0.33gAM,17 mu L of polyethylene glycol diacrylate (accounting for 0.3 percent of the total mole of monomers) and 4 mu L of 2-hydroxy-2-methyl-1-phenylpropionic acid (accounting for 0.3 percent of the total mole of monomers) are placed in a clean 25ml beaker, and after the rotator is added, the mixture is placed on a magnetic workbench and stirred for 10 minutes at a stirring speed of 700 r/min. The above mixed solution was injected into two 3 x 3cm glass plates with a thickness of 2mm between the plates using a 2mL syringe. After the solution is injected, small bubbles in the glass plate are emptied, the glass plate is placed in an ultraviolet curing box with the wavelength of 365nm for irradiation for 15min, after the temperature of the glass plate is cooled to room temperature, the hydrogel is taken out, and sample S is numbered 2 A 3 Placing into a self-sealing bag for preservation.
Example 2
0.6g of imidazole cation salt is weighed at room temperature, 3.9ml of water is added to prepare 1mol/L solution, 0.63g SBMA,0.33gAM,21 mu L of polyethylene glycol diacrylate (accounting for 0.3 percent of the total mole of monomers) and 5 mu L of 2-hydroxy-2-methyl-1-phenylpropionic acid (accounting for 0.3 percent of the total mole of monomers) are placed in a clean 25ml beaker, and after the rotor is added, the mixture is placed on a magnetic workbench and stirred for 10 minutes at a stirring speed of 700 r/min. The above mixed solution was injected into two 3 x 3cm glass plates with a thickness of 2mm between the plates using a 2mL syringe. After the solution is injected, small bubbles in the glass plate are emptied, the glass plate is placed in an ultraviolet curing box with the wavelength of 365nm for irradiation for 15min, after the temperature of the glass plate is cooled to room temperature, the hydrogel is taken out, and sample S is numbered 3 A 3 Placing into a self-sealing bag for preservation.
Example 3
0.6g of imidazole cation salt is weighed at room temperature, 3.9ml of water is added to prepare 1mol/L solution, 0.84g SBMA,0.33gAM,25 mu L of polyethylene glycol diacrylate (accounting for 0.3 percent of the total mole of monomers) and 6 mu L of 2-hydroxy-2-methyl-1-phenylpropionic acid (accounting for 0.3 percent of the total mole of monomers) are placed in a clean 25ml beaker, and the mixture is placed on a magnetic workbench to be stirred for 10 minutes at a stirring speed of 700r/min after a rotator is added. The above mixed solution was injected into two 3 x 3cm glass plates with a thickness of 2mm between the plates using a 2mL syringe. After the solution is injected, small bubbles in the glass plate are emptied, the glass plate is placed in an ultraviolet curing box with the wavelength of 365nm for irradiation for 15min, after the temperature of the glass plate is cooled to room temperature, the hydrogel is taken out, and sample S is numbered 4 A 3 Placing into a self-sealing bag for preservation.
Example 4
The preparation process is the same as in example 1, except that: the mass of SBMA and AM added was 0.63g and 0.11g respectively, and the obtained zwitterionic hydrogels were designated as sample S 3 A 1 。
Example 5
The preparation process is the same as in example 1, except that: the mass of SBMA and AM added was 0.63g and 0.165g respectively, and the obtained zwitterionic hydrogels were designated as sample S 3 A 1.5 。
Example 6
The preparation process is the same as in example 1, except that: the mass of SBMA and AM added was 0.63g and 0.22g respectively, and the obtained zwitterionic hydrogels were designated as sample S 3 A 2 。
Example 7
The preparation process is the same as in example 1, except that: the mass of SBMA and AM added was 0.63g and 0.275g respectively, and the resulting zwitterionic hydrogels were designated as sample S 3 A 2.5 。
Analytical example 1 unidirectional tensile test
The test method is as follows:
1. taking zwitterionic hydrogel as a dumbbell-shaped sample with the length of 3cm and the width of 0.1cm, clamping the clamps at the two ends by 0.9cm respectively, reserving the middle 1.2cm as an experimental area, and carrying out unidirectional stretching on the sample on a universal tensile testing machine, wherein the stretching speed is set to be 50mm/min.
The toughness of the hydrogels was calculated from the integrated area of the stress-strain curve and the elastic modulus was calculated from the initial slope of the stress-strain curve (strain in the range of 0% -20%).
As shown in fig. 2 and 3, the tensile test results show that: with the increase of SBMA content, the strain of the hydrogel is continuously increased, and the maximum strain can reach 1170%. With increasing AM content, the stress of the hydrogel is continuously increased, and the maximum value can reach 341kPa.
Analytical example 2 cyclic unidirectional tensile test
The test method is as follows:
the hydrogel was subjected to a tensile cycle test using the same universal stretcher at room temperature, and all hydrogel samples were cut into dumbbell-shaped bars of length, width, and thickness 10mm, 5mm, and 1mm, respectively. In the test, the maximum strain of the stretching cycle was set to 200%, the stretching speed was set to 100mm/min, and the number of cycles was 10.
In addition, the dissipation energy of the hydrogels was calculated from the integrated area of the tensile cycle curve and the elastic modulus was calculated from the initial slope of the tensile cycle curve (strain in the range of 0% -20%).
Analytical example 3 self-healing Performance test
Will prepare S 3 A 3 The hydrogel is cut with a sharp blade, the split hydrogels are contacted with each other with gentle force to promote the self-healing process, and finally the hydrogel is repaired by placing the hydrogel in an environment with a constant temperature of 37 ℃ and a relative humidity of about 80% -90%. Fig. 4A is a digital photograph of a hydrogel after self-healing using methyl orange and brilliant green staining. The repaired hydrogel is subjected to a tensile test, as shown in fig. 4B, the tensile property of the hydrogel is continuously recovered along with the increase of the repair time, and the repair efficiency after 24 hours reaches 80%, which fully shows that the hydrogel has reliable self-healing property. After the hydrogel is severed, internal hydrogen bonding and electrostatic forces are partially destroyed, and when placed in a constant temperature and relatively humid environment, the polymer segments interpenetrate entanglement at the fracture sites and the energy of the dynamic bonds is dissipated to enable the hydrogel to spontaneously repair the injury.
Analytical example 4 conductive and sensing Properties investigation
The conductivity of the hydrogels was measured by a digital four-probe tester (ST 2258C, china). The electrochemical properties of the hydrogels were measured using a four electrode ac impedance method and the hydrogels were cut into samples 30mm long, 10mm wide and 1mm thick. The conductivity (σS/cm) was calculated as: sigma=l/(r×s), where L (cm) is the distance between the two probes, R (Ω) is the resistance of the hydrogel, S (cm) -2 ) Is the cross-sectional area of the hydrogel. The change in resistance of the hydrogel was recorded by using an electrochemical analyzer/workstation (CHI 600E, china). The resistance value was calculated according to ohm's law (r=u/I), a constant voltage of 0.1V was applied to the hydrogel, and the relative resistance change caused by different strains was expressed as gf= [ (R-R0)/R0]= (Δr/R0)/epsilon, where R0 and R are the electrical resistance of the original and stretched hydrogel, respectively, and epsilon is the strain of the hydrogel. FIG. 5A is a graph showing the relative resistance change (ΔR/R0) of a hydrogel during stretching; fig. 5B shows the relative resistance change of a hydrogel stretched 150 times over cycles at 20% strain. Indicating the high sensitivity and reproducibility of hydrogels.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (9)
1. The zwitterionic polymer hydrogel is characterized by being formed by crosslinking a cationic imidazole salt, a zwitterionic monomer and an amide compound through dynamic covalent bonds and non-covalent bonds; the non-covalent bond includes electrostatic and hydrogen bonding;
the preparation method of the zwitterionic polymer hydrogel comprises the following steps: photoinitiating a mixture containing a zwitterionic monomer, an amide compound, a cross-linking agent, cationic imidazole and a photoinitiator to obtain the zwitterionic hydrogel;
wherein the cationic imidazole salt is at least one selected from cationic imidazole sodium salt and cationic imidazole potassium salt; the cationic imidazole salt is added in the form of an aqueous solution, and the concentration of the cationic imidazole salt in the aqueous solution is 1 mol/L-3 mol/L;
the zwitterionic monomer is a betaine type amphoteric surfactant;
the amide compound is at least one selected from acrylamide and N-vinyl caprolactam;
the cross-linking agent is at least one selected from polyethylene glycol diacrylate and N, N' -methylene bisacrylamide;
the photoinitiator is selected from aromatic ketone compounds;
the molar ratio of the cationic imidazole salt to the zwitterionic monomer to the amide compound is 1-2: 1-4:1-4.
2. The zwitterionic polymer hydrogel of claim 1, wherein the zwitterionic polymer hydrogel has a maximum strain of 1155% to 1172%.
3. The zwitterionic polymer hydrogel of claim 1, wherein the zwitterionic polymer hydrogel has a maximum stress of from 337kPa to 346kPa.
4. The zwitterionic polymer hydrogel of claim 1, wherein the betaine-type amphoteric surfactant is selected from one of a carboxylic acid betaine and a sulfobetaine.
5. The zwitterionic polymer hydrogel of claim 4, wherein the carboxybetaines are selected from one of carboxybetaines methacrylate, acryloylethylcarboxybetaines; the sulfobetaine is selected from one of methacrylic acid sulfobetaine and acryloylethyl sulfobetaine.
6. The zwitterionic polymer hydrogel of claim 1, wherein the aromatic ketone compound is selected from at least one of 2-hydroxy-2-methyl-1-phenylpropion, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropionacetone.
7. The zwitterionic polymer hydrogel of claim 1, wherein the crosslinker is present in an amount of from 0.1% to 0.5% of the molar total amount of the zwitterionic monomer and the amide;
the dosage of the photoinitiator is 0.1-0.5% of the molar total amount of the zwitterionic monomer and the cationic imidazole salt.
8. The zwitterionic polymer hydrogel of claim 1, wherein the photoinitiating conditions are as follows: the light source is ultraviolet light, and the wavelength of the ultraviolet light is 320 nm-365 nm; the reaction time is 10 min-20 min.
9. Use of the zwitterionic polymer hydrogel according to any one of claims 1 to 8 in flexible electronics, wearable devices, stretchable bioelectronics, electronic detection instrument stickers, medical adhesives.
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| CN110372885A (en) * | 2019-06-28 | 2019-10-25 | 浙江工业大学 | A kind of chitosan/amphoteric ion and acrylic copolymer dual network self-healing hydrogel and preparation method thereof |
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| CN113150214A (en) * | 2021-04-28 | 2021-07-23 | 青岛科技大学 | Preparation method of self-repairing antibacterial hydrogel containing imidazolium salt |
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| CN110372885A (en) * | 2019-06-28 | 2019-10-25 | 浙江工业大学 | A kind of chitosan/amphoteric ion and acrylic copolymer dual network self-healing hydrogel and preparation method thereof |
| CN111363172A (en) * | 2020-04-06 | 2020-07-03 | 刘云晖 | Preparation method of self-healing zwitterionic hydrogel |
| CN111925476A (en) * | 2020-07-17 | 2020-11-13 | 浙江工业大学 | Conductive antibacterial hydrogel and preparation method and application thereof |
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